US4637467A - Permeability contrast correction - Google Patents
Permeability contrast correction Download PDFInfo
- Publication number
- US4637467A US4637467A US06/755,750 US75575085A US4637467A US 4637467 A US4637467 A US 4637467A US 75575085 A US75575085 A US 75575085A US 4637467 A US4637467 A US 4637467A
- Authority
- US
- United States
- Prior art keywords
- process according
- water
- acrylamide
- vinyl
- permeability
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 230000035699 permeability Effects 0.000 title claims abstract description 35
- 238000012937 correction Methods 0.000 title claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 57
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims abstract description 46
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 30
- 238000011065 in-situ storage Methods 0.000 claims abstract description 24
- 150000003926 acrylamides Chemical class 0.000 claims abstract description 16
- -1 diacetone acrylamide Chemical class 0.000 claims abstract description 14
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 13
- 229920003176 water-insoluble polymer Polymers 0.000 claims abstract description 13
- 238000002347 injection Methods 0.000 claims abstract description 11
- 239000007924 injection Substances 0.000 claims abstract description 11
- 150000001408 amides Chemical class 0.000 claims abstract description 7
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 150000002825 nitriles Chemical class 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- 150000003871 sulfonates Chemical class 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 25
- 239000003999 initiator Substances 0.000 claims description 22
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 11
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- 229920001519 homopolymer Polymers 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000012267 brine Substances 0.000 claims description 3
- 150000001451 organic peroxides Chemical class 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 3
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 claims description 2
- 125000006025 1-methyl-1-butenyl group Chemical group 0.000 claims description 2
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 claims description 2
- 125000006027 3-methyl-1-butenyl group Chemical group 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000007870 radical polymerization initiator Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 5
- 239000003792 electrolyte Substances 0.000 claims 2
- CCTFAOUOYLVUFG-UHFFFAOYSA-N 2-(1-amino-1-imino-2-methylpropan-2-yl)azo-2-methylpropanimidamide Chemical compound NC(=N)C(C)(C)N=NC(C)(C)C(N)=N CCTFAOUOYLVUFG-UHFFFAOYSA-N 0.000 claims 1
- PGFZYOCLSPEKSN-UHFFFAOYSA-N 5,5-dimethyl-1,3-diazabicyclo[2.2.0]hex-3-ene dihydrochloride Chemical compound Cl.Cl.CC1(C)CN2CN=C12 PGFZYOCLSPEKSN-UHFFFAOYSA-N 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 35
- 238000005755 formation reaction Methods 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 21
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 11
- 239000012530 fluid Substances 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 101100490446 Penicillium chrysogenum PCBAB gene Proteins 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000013535 sea water Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 241000237858 Gastropoda Species 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 3
- AZCYBBHXCQYWTO-UHFFFAOYSA-N 2-[(2-chloro-6-fluorophenyl)methoxy]benzaldehyde Chemical compound FC1=CC=CC(Cl)=C1COC1=CC=CC=C1C=O AZCYBBHXCQYWTO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000005465 channeling Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000010952 in-situ formation Methods 0.000 description 2
- 230000037230 mobility Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 1
- HSMAVZYQDXUJLK-UHFFFAOYSA-N 2-(tert-butyldiazenyl)-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C)C HSMAVZYQDXUJLK-UHFFFAOYSA-N 0.000 description 1
- JZDHUYKBYNFYAB-UHFFFAOYSA-N 2-(tert-butyldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(C)C JZDHUYKBYNFYAB-UHFFFAOYSA-N 0.000 description 1
- PYKCEDJHRUUDRK-UHFFFAOYSA-N 2-(tert-butyldiazenyl)-2-methylpropanenitrile Chemical compound CC(C)(C)N=NC(C)(C)C#N PYKCEDJHRUUDRK-UHFFFAOYSA-N 0.000 description 1
- XYDCNXPXPVLOPD-UHFFFAOYSA-N 2-(tert-butyldiazenyl)-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C)C XYDCNXPXPVLOPD-UHFFFAOYSA-N 0.000 description 1
- WGUWOLAXPCRPKH-UHFFFAOYSA-N 2-(tert-butyldiazenyl)cyclohexane-1-carbonitrile Chemical compound CC(C)(C)N=NC1CCCCC1C#N WGUWOLAXPCRPKH-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical group COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LPIJERWHZYVVLP-UHFFFAOYSA-N 4-(tert-butyldiazenyl)-4-cyanopentanoic acid Chemical compound CC(C)(C)N=NC(C)(C#N)CCC(O)=O LPIJERWHZYVVLP-UHFFFAOYSA-N 0.000 description 1
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 1
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-M ethenesulfonate Chemical compound [O-]S(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-M 0.000 description 1
- PWHMFVALYNYYMZ-UHFFFAOYSA-N ethenyl phenylmethanesulfonate;sodium Chemical compound [Na].C=COS(=O)(=O)CC1=CC=CC=C1 PWHMFVALYNYYMZ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- NFMHSPWHNQRFNR-UHFFFAOYSA-N hyponitrous acid Chemical class ON=NO NFMHSPWHNQRFNR-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- VFQNTYSGSZZOHH-UHFFFAOYSA-N n-(2,3,7-trimethyl-5-oxooctan-3-yl)prop-2-enamide Chemical compound CC(C)CC(=O)CC(C)(C(C)C)NC(=O)C=C VFQNTYSGSZZOHH-UHFFFAOYSA-N 0.000 description 1
- IIPKOXQPWUAIAI-UHFFFAOYSA-N n-(3,4-dimethyl-5-oxohexan-3-yl)prop-2-enamide Chemical compound CC(=O)C(C)C(C)(CC)NC(=O)C=C IIPKOXQPWUAIAI-UHFFFAOYSA-N 0.000 description 1
- ZSASUEHVABIIIF-UHFFFAOYSA-N n-(3-oxobutyl)prop-2-enamide Chemical compound CC(=O)CCNC(=O)C=C ZSASUEHVABIIIF-UHFFFAOYSA-N 0.000 description 1
- XDQZDULETXHECC-UHFFFAOYSA-N n-(3-oxopropyl)prop-2-enamide Chemical compound C=CC(=O)NCCC=O XDQZDULETXHECC-UHFFFAOYSA-N 0.000 description 1
- DOPQONDTFJCCME-UHFFFAOYSA-N n-(4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)NC(=O)C=C DOPQONDTFJCCME-UHFFFAOYSA-N 0.000 description 1
- YSCPIQWZZANCAT-UHFFFAOYSA-N n-[(2-methylpropan-2-yl)oxy]nitrous amide Chemical compound CC(C)(C)ONN=O YSCPIQWZZANCAT-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- ISHQXKNXUUTBOY-UHFFFAOYSA-M sodium;(4-ethenylphenyl)methanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC1=CC=C(C=C)C=C1 ISHQXKNXUUTBOY-UHFFFAOYSA-M 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Definitions
- This invention relates generally to the recovery of oil from subterranean oil-bearing formations. In one aspect it relates to a method for polymerizing water-soluble monomers to water-insoluble polymers in a subterranean formation. In accordance with a further aspect, this invention relates to a process for the selective plugging of permeable subterranean strata by in situ polymerization of water-soluble monomers that are polymerized to water-insoluble polymers. In still another aspect, this invention relates to a method for correcting the water permeability of subterranean formations. In still another aspect, this invention relates to a method for reducing the permeability of subterranean formations, thereby promoting better control of fluid injection patterns and improving the enhanced recovery of hydrocarbons.
- an object of this invention is to provide an improved process for the recovery of oil from subterranean oil-bearing formations.
- Another object of this invention is to selectively plug high permeability zones in subterranean formations.
- Another object of this invention is to increase sweep efficiency of post-primary or enhanced oil recovery operations.
- DAAM water-insoluble diacetone acrylamide
- permeability contrast correction operations involve the in situ polymerization of water-soluble monomers, such as acrylamide (Am), and diacetone acrylamide (DAAm) to form water-insoluble polymers.
- water-soluble monomers such as acrylamide (Am), and diacetone acrylamide (DAAm)
- water-soluble monomers exhibit a water solubility of not less than 5 g of monomer per 100 mL of water 20° C.
- the invention is applicable to any situation where it is desired to selectively plug the more permeable zones in subterranean formations.
- the invention is directed to selective plugging of more permeable zones known as "thief" zones to improve the sweep efficiency of post-primary or enhanced oil recovery processes.
- the plug forming materials of this invention are generated in situ from water-soluble monomers that upon polymerization form water-insoluble polymers. Accordingly, the invention involves injecting into subterranean formations water-soluble monomers and at least one polymerization initiator and carrying out polymerization of the injected water-soluble monomers in the formation under conditions to form insoluble polymers which plug the more permeable portions of the formation.
- polymers is used generically unless otherwise indicated to mean homopolymers and copolymers prepared from water-soluble monomers wherein a major portion of the monomer(s) is an N-3-oxohydrocarbon-substituted arylamide, preferably diacetone acrylamide (DAAm), viz., N-3-oxo-1,1-dimethyl-butyl acrylamide.
- DAAm diacetone acrylamide
- Homopolymers of N-3-oxohydrocarbon-substituted acrylamides prepared in accordance with this invention are water-insoluble and maintain their properties even under adverse conditions such as high temperature, high salinity and/or high concentrations of "hardness" ions.
- Homopolymers of this invention are derived from monomer units of N-3-oxohydrocarbon-substituted acrylamides having the structural formula ##STR1## wherein R and R 2 are each selected from the class consisting of hydrogen and lower alkyl radicals and R 1 is selected from the class consisting of ethylene and lower alkyl-substituted ethylene radicals.
- the lower alkyl radicals are those containing no more than about 6 carbon atoms with the proviso that the monomers contain 6 to 14 carbon atoms.
- Radicals are exemplified by methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, n-pentyl, cyclohexyl and cyclopentyl radicals.
- N-3-oxohydrocarbon-substituted acrylamide monomers and polymers are disclosed in U.S. Pat. No. 3,277,056 which is incorporated herein by reference.
- N-3-oxohydrocarbon-substituted acrylamides include
- the diacetone acrylamide (DAAm) copolymers of this invention are produced by copolymerizing a major proportion of at least one N-3-oxohydrocarbon-substituted acrylamide with a minor amount of at least one comonomer selected from N-vinyl amides having the formula ##STR2## wherein R' 2 , R 3 and R 4 are selected independently from the group consisting of hydrogen and methyl and R 1 is selected from C 1 to C 3 alkyl groups.
- the groups R' 1 , and R' 2 can collectively represent linear or branched divalent alkylene groups containing 2 to 4 carbon atoms. These monomers are generally water-soluble or water-dispersible.
- a more preferred class of compounds are those of the formula ##STR3## wherein R is hydrogen, methyl or ethyl.
- the monomer unit presently most preferred is N-vinyl-2-pyrrolidone.
- the water insoluble copolymers of this invention can also be produced by copolymerizing a major proportion of at least one hydrocarbon substituted acrylamide with a minor amount of at least one comonomer selected from unsaturated amides having the formula ##STR4## wherein R 5 is a 1-alkenyl radical selected from the group ethenyl(vinyl), 1-propenyl, 2-propenyl, 1-butenyl, 2-methyl-1-propenyl, 1-pentenyl, 3-methyl-1-butenyl, and 1-methyl-1-butenyl.
- R 5 is a 1-alkenyl radical selected from the group ethenyl(vinyl), 1-propenyl, 2-propenyl, 1-butenyl, 2-methyl-1-propenyl, 1-pentenyl, 3-methyl-1-butenyl, and 1-methyl-1-butenyl.
- VP N-vinyl-2-pyrrolidone
- Am acrylamide
- a more preferred class of alpha,beta-unsaturated amide comonomers for polymerization with diacetone acrylamide is described by the formula ##STR5## wherein each R 6 is individually selected from H and methyl.
- Especially suitable in addition to acrylamide are N-methylacrylamide and N,N-dimethylacrylamide (DMAm).
- Another class of comonomers that can be used for polymerization with diacetone acrylamide includes alpha-beta-unsaturated nitriles, e.g., acrylonitrile, methacrylonitrile and the like.
- Diacetone acrylamides can also be polymerized with a minor amount of another comonomer referred to as a vinyl-containing sulfonate which is meant to encompass the acid also.
- a vinyl-containing sulfonate which is meant to encompass the acid also.
- They are represented by the following formula ##STR6## wherein R' is methyl, ethyl or H preferably methyl or H and provided further that at least one of the R' groups on the terminal carbon of the vinyl group is H and the other is H or methyl; M is H, Na + , K + , Li + , R" 4 N + , Ca ++ or Mg ++ and X is ##STR7## wherein n is an integer of 1-5 preferably 1-3 and R" is a 1-3 carbon atom alkyl group or H.
- suitable monomers include:
- vinyl sulfonate sodium salt ##STR8## sodium 2-acrylamido-2-methylpropanesulfonate (NaAMPS) ##STR9## styrene sulfonate, sodium salt ##STR10## sodium vinyl toluene sulfonate ##STR11## sodium p-vinylbenzyl sulfonate
- the relative proportions of the water-soluble diacetone acrylamide monomer and the water-soluble comonomers that can be used depend upon the reactivity of these monomers as well as the desired properties of the resulting water-insoluble polymers. It has been found, however, that the amount of diacetone acrylamide present in the copolymers ranges from about 40 to about 95 weight percent of the polymer composition.
- the water-insoluble polymers of the invention comprise a major amount of at least one N-3-oxohydrocarbon-substituted acrylamide and preferably from about 60 to 100 weight percent diacetone acrylamide (DAAm) with the balance in copolymers being formed from at least one other water-soluble monomer.
- DAAm diacetone acrylamide
- the polymers of this invention can be formd in situ by injecting monomer solutions containing polymerization initiators into subterranean formations.
- the feasibility of polymerizing the monomers in situ, e.g., in saline connate waters is supported by the success of laboratory runs in Berea sandstone cores wherein the cores were plugged by injecting solutions of monomers and initiators.
- the cores were saturated with brine containing appropriate dissolved salts, such as found in sea water, to provide a simulated or synthetic sea water (SSW). Natural sea water and formation brines can also be used as the polymerization media in the core runs.
- SSW simulated or synthetic sea water
- Various field brines containing a high percentage of dissolved solids can be diluted with fresh water to provide an appropriate concentration of dissolved solids for lab core tests.
- salts can be added to various field brines, if deemed necessary, to obtain the desired salt level.
- Oil field brines can be used as polymerization media in lab core runs. Such brines can be filtered or otherwise purified to remove undesirable solid matter before use in lab runs. Oil field brines can contain up to about 25 percent by weight of dissolved inorganic salts. In addition to NaCl, brines usually contain up to about 10 percent by weight of Ca ++ and Mg ++ based on the total amount of salts present. Small amounts of other soluble salts are also frequently present, e.g., NaHCO 3 , BaCl 2 , and the like. Typical brines contain from about 1 to about 14 weight percent dissolved salts based on water.
- sea water would be the preferred polymerization medium to use in simulated lab core runs.
- Sea water may require a preliminary treatment such as simple filtration to render it suitable for use as a polymerization medium in a laboratory core test.
- the polymers of this invention can be prepared by processes using various free radical polymerization initiators known to those skilled in the art.
- Preferred initiators for the instant invention include chemical polymerization initiators.
- Chemical polymerization initiators suitable for the inventive in situ polymerization process include azo compounds and organic peroxides such as 2,2'-azobis(isobutyronitrile) (commercially available as Vazo-64® from E. I. DuPont); 2-t-butylazo-2-cyanopropane, 2,2'-azobis(2,4-dimethylvaleronitrile) (Vazo-52® from E. I.
- a particularly suitable lower temperature initiator is 2,2'-azobis(2,4-dimethyl-4-methoxy-valeronitrile) commercially available as Vazo 33 from E. I. DuPont.
- Presently preferred initiators include t-butyl peroxypivalate (t-BPP), Luazo 55, Luazo 70, p-menthane hydroperoxide activated by FeSO 4 .7H 2 O and especially 2,2'-azobis(isobutyronitrile) (AIBN).
- t-BPP t-butyl peroxypivalate
- Luazo 55 Luazo 55
- Luazo 70 p-menthane hydroperoxide activated by FeSO 4 .7H 2 O
- AIBN 2,2'-azobis(isobutyronitrile)
- the use of these initiators usually results in the production of higher molecular weight polymers, Luazo 70 has been found to give excellent results because, as a liquid, it is more uniformly dispersible in water than are solid initiators such as AI
- Luazo 55 is also a liquid and possesses the same advantage.
- the amidine type initiators and the 4-cyanovaleric acid initiators are preferred because they are water soluble.
- An inert atmosphere substantially free of oxygen or other known inhibiting materials should be provided when chemical polymerization initiators are used.
- Chemical polymerization initiators which are substantially soluble in the polymerization media of this invention are advantageously used because they can be dissolved in the monomer solution or dispersed in a small amount of solvent which is miscible or soluble in the monomer solution therein before the monomer solution is injected into the subterranean formation.
- Chemical polymerization initiators which are insufficiently soluble in the monomer solution of this invention in the concentration required for initiation can be added in the commercially available state or dispersed as a fine powder but are generally more effectively employed if first dissolved in a liquid which is soluble in or miscible with the monomer mixture.
- a water-miscible solvent such as acetone or an alcohol can be used to solubilize 2,2'-azobis(isobutyronitrile), the preferred chemical initiator, and to disperse it in the aqueous monomer mixture.
- a chemical initiator based on total monomer weight is used for chemical initiation.
- the appropriate initiator is selected based on the temperature of the subterranean formation to be treated. For example, at a formation temperature of about 170 F., the initiator should have a half-life of at least several hours at 120 F.
- the in situ polymerization of this invention is applicable to any situation where it is desired to selectively plug more permeable zones in subterranean formations by in situ polymerization of water-soluble monomers to form water-insoluble polymers.
- the invention is primarily directed to the selective plugging of the more permeable zones known as "thief" zones to improve the sweep efficiency of post-primary oil recovery processes.
- one or more water-soluble monomers are injected as an aqueous slug into a subterranean formation passing predominantly into the more permeable zones of the formation wherein the monomers polymerize in situ and form water-insoluble polymers.
- Polymerization initiators can be injected preferably along with monomer(s). Alternatively, the initiators can be injected subsequently or prior to monomer injection.
- Epoxy wrapped Berea sandstone cores (1" diameter ⁇ 3 inches long) which were equipped with pressure taps 1 centimeter from the face were evacuated, saturated and then pressure saturated with synthetic North Sea water (SNSW).
- the Berea cores were waterflooded at 150 F., with SNSW until a constant permeability was obtained.
- the core was oilflooded with crude NBU oil before waterflooding to residual oil saturation.
- the cores were generally conditioned in this manner before the injection of the monomer slugs containing polymerization initiators.
- the effectiveness of the instant process can be expected to be greater for water soluble monomer(s) systems resulting in the production of insoluble polymers.
- copolymers of diacetone acrylamide (DAAm) with VP or Am containing in the range of 40 to 95 weight percent DAAm are water insoluble, it is contemplated that copolymers of DAAm/VP and DAAm/Am can be advantageously used in the instant process.
- Representative copolymers of DAAm and Am exhibit a tendency to swell and therefore are presently preferred in the instant permeability contrast correction process.
- Suitable water-soluble comonomers to be used in conjunction with DAAm include VP, Am, sodium 2-acrylamido-2-methylpropanesulfonate (NaAMPS) and acrylonitrile (An) wherein the designation water soluble comonomer indicates that said comonomers exhibit solubilities of 5 or more grams of comonomer per 100 mL of water at 20° C.
Abstract
Polymerization in-situ to effect permeability contrast correction in oil-bearing subterranean formations comprising the injection of at least one water-soluble monomer comprising N-3-oxohydrocarbon-substituted acrylamides, such as diacetone acrylamide, and optionally at least one water-soluble comonomer, such as alpha,beta-unsaturated amides, alpha,beta-unsaturated nitriles, vinyl-containing sulfonates and N-vinyl amides and polymerization initiator to cause polymerization and formation of water-insoluble polymers in high permeability zones.
Description
This invention relates generally to the recovery of oil from subterranean oil-bearing formations. In one aspect it relates to a method for polymerizing water-soluble monomers to water-insoluble polymers in a subterranean formation. In accordance with a further aspect, this invention relates to a process for the selective plugging of permeable subterranean strata by in situ polymerization of water-soluble monomers that are polymerized to water-insoluble polymers. In still another aspect, this invention relates to a method for correcting the water permeability of subterranean formations. In still another aspect, this invention relates to a method for reducing the permeability of subterranean formations, thereby promoting better control of fluid injection patterns and improving the enhanced recovery of hydrocarbons.
In post-primary oil recovery operations, recovery of oil is maximized if the driven fluid is permitted to build up in a wide bank in front of the driving fluid which moves uniformly toward a producing well. To keep this bank of oil intact while moving toward a producing well, a substantially uniform permeability must exist throughout the strata. If this uniform permeability does not exist, and it generally does not, the flooding fluids will seek the areas of high permeability and channeling occurs with the appearance of excess driving fluid at the producing well. Moreover, as the more permeable strata are depleted of oils, the driving fluid has a tendency to follow these channels and further increase water production as reflected in an increased water-to-oil ratio at producing wells to the point that the process becomes economically undesirable.
It is known in the art that more uniform flood fronts can be obtained in formations of non-uniform permeability by mobility control or permeability contrast correction of the more permeable strata in the formation. A number of methods for reducing the permeability of these permeable strata have been proposed, including the injection of plugging materials into the strata which at least partially plug the permeable zones so as to achieve more uniform permeability. Some of these methods of permeability contrast correction accomplish the plugging step by the in situ formation of plugging material in the formation by the injection of one or more reaction substances which chemically react to form a solid residue. The present invention is directed to the in situ formation of water-insoluble polymers from water-soluble monomers in a manner such that selective plugging of the formation is achieved.
Accordingly, an object of this invention is to provide an improved process for the recovery of oil from subterranean oil-bearing formations.
Another object of this invention is to selectively plug high permeability zones in subterranean formations.
Another object of this invention is to increase sweep efficiency of post-primary or enhanced oil recovery operations.
Other aspects, objects and the several advantages of this invention will become readily apparent to those skilled in the art from a reading of the following detailed description of the invention and the appended claims.
In accordance with the invention, it has been found that high permeability strata in subterranean formations can be selectively plugged by in situ polymerization of water-soluble monomers to form water-insoluble polymers to effectively minimize channeling of injected fluid, into high permeability strata.
In accordance with one embodiment of this invention, it has been found that water-insoluble diacetone acrylamide (DAAM) homopolymer and selected water-insoluble copolymers of DAAM formed by in situ polymerization in high permeability strata in subterranean formations are effective for permeability contrast correction.
In accordance with a specific embodiment of this invention, permeability contrast correction operations involve the in situ polymerization of water-soluble monomers, such as acrylamide (Am), and diacetone acrylamide (DAAm) to form water-insoluble polymers. Copolymers containing on the order of 40 to 95 weight percent diacetone acrylamide and at least one other water-soluble monomer such as acrylamide and N-vinyl-2-pyrrolidone (VP) are water insoluble and are, therefore, suitable for use in the instant process. In this application, water-soluble monomers exhibit a water solubility of not less than 5 g of monomer per 100 mL of water 20° C.
The invention is applicable to any situation where it is desired to selectively plug the more permeable zones in subterranean formations. Primarily, the invention is directed to selective plugging of more permeable zones known as "thief" zones to improve the sweep efficiency of post-primary or enhanced oil recovery processes.
The plug forming materials of this invention are generated in situ from water-soluble monomers that upon polymerization form water-insoluble polymers. Accordingly, the invention involves injecting into subterranean formations water-soluble monomers and at least one polymerization initiator and carrying out polymerization of the injected water-soluble monomers in the formation under conditions to form insoluble polymers which plug the more permeable portions of the formation.
As used herein, the term "polymers" is used generically unless otherwise indicated to mean homopolymers and copolymers prepared from water-soluble monomers wherein a major portion of the monomer(s) is an N-3-oxohydrocarbon-substituted arylamide, preferably diacetone acrylamide (DAAm), viz., N-3-oxo-1,1-dimethyl-butyl acrylamide.
Homopolymers of N-3-oxohydrocarbon-substituted acrylamides prepared in accordance with this invention are water-insoluble and maintain their properties even under adverse conditions such as high temperature, high salinity and/or high concentrations of "hardness" ions.
Homopolymers of this invention are derived from monomer units of N-3-oxohydrocarbon-substituted acrylamides having the structural formula ##STR1## wherein R and R2 are each selected from the class consisting of hydrogen and lower alkyl radicals and R1 is selected from the class consisting of ethylene and lower alkyl-substituted ethylene radicals. The lower alkyl radicals are those containing no more than about 6 carbon atoms with the proviso that the monomers contain 6 to 14 carbon atoms. Radicals are exemplified by methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, n-pentyl, cyclohexyl and cyclopentyl radicals.
The N-3-oxohydrocarbon-substituted acrylamide monomers and polymers are disclosed in U.S. Pat. No. 3,277,056 which is incorporated herein by reference.
Specific examples of the N-3-oxohydrocarbon-substituted acrylamides include
N-3-oxopropyl acrylamide,
N-3-oxobutyl acrylamide,
N-3-oxo-1-methyl-butyl acrylamide,
N-3-oxo-1,1-dimethyl-butyl acrylamide,
N-3-oxo-1,2-dimethyl-1-ethyl-butyl acrylamide,
N-3-oxo-1,5-dimethyl-1-isopropyl-hexyl acrylamide,
and N-3-oxo-1-methyl-butyl alpha-methyl acrylamide,
The diacetone acrylamide (DAAm) copolymers of this invention are produced by copolymerizing a major proportion of at least one N-3-oxohydrocarbon-substituted acrylamide with a minor amount of at least one comonomer selected from N-vinyl amides having the formula ##STR2## wherein R'2, R3 and R4 are selected independently from the group consisting of hydrogen and methyl and R1 is selected from C1 to C3 alkyl groups. The groups R'1, and R'2 can collectively represent linear or branched divalent alkylene groups containing 2 to 4 carbon atoms. These monomers are generally water-soluble or water-dispersible.
A more preferred class of compounds are those of the formula ##STR3## wherein R is hydrogen, methyl or ethyl. The monomer unit presently most preferred is N-vinyl-2-pyrrolidone.
The water insoluble copolymers of this invention can also be produced by copolymerizing a major proportion of at least one hydrocarbon substituted acrylamide with a minor amount of at least one comonomer selected from unsaturated amides having the formula ##STR4## wherein R5 is a 1-alkenyl radical selected from the group ethenyl(vinyl), 1-propenyl, 2-propenyl, 1-butenyl, 2-methyl-1-propenyl, 1-pentenyl, 3-methyl-1-butenyl, and 1-methyl-1-butenyl. These alpha,beta-unsaturated amides are generally water-soluble or water-dispersible.
The comonomers presently preferred for polymerization with diacetone acrylamide (DAAm) are N-vinyl-2-pyrrolidone (VP) and acrylamide (Am). For convenience, the terms VP and Am will be used to refer to these comonomers, respectively, in the discussions herein.
A more preferred class of alpha,beta-unsaturated amide comonomers for polymerization with diacetone acrylamide is described by the formula ##STR5## wherein each R6 is individually selected from H and methyl. Especially suitable in addition to acrylamide are N-methylacrylamide and N,N-dimethylacrylamide (DMAm).
Another class of comonomers that can be used for polymerization with diacetone acrylamide includes alpha-beta-unsaturated nitriles, e.g., acrylonitrile, methacrylonitrile and the like.
Diacetone acrylamides can also be polymerized with a minor amount of another comonomer referred to as a vinyl-containing sulfonate which is meant to encompass the acid also. They are represented by the following formula ##STR6## wherein R' is methyl, ethyl or H preferably methyl or H and provided further that at least one of the R' groups on the terminal carbon of the vinyl group is H and the other is H or methyl; M is H, Na+, K+, Li+, R"4 N+, Ca++ or Mg++ and X is ##STR7## wherein n is an integer of 1-5 preferably 1-3 and R" is a 1-3 carbon atom alkyl group or H. Examples of suitable monomers include:
H.sub.2 C=CH--SO.sub.3 NA
vinyl sulfonate, sodium salt ##STR8## sodium 2-acrylamido-2-methylpropanesulfonate (NaAMPS) ##STR9## styrene sulfonate, sodium salt ##STR10## sodium vinyl toluene sulfonate ##STR11## sodium p-vinylbenzyl sulfonate
These are known monomers and can be produced as is known in the art. Particularly with regard to the N-sulfohydrocarbon-substituted acrylamides, they are disclosed in U.S. Pat. No. 3,679,000 assigned to the Lubrizol Corporation, the disclosure of which patent is incorporated by reference. The 2-acrylamido-2-methylpropane sulfonic acid is available from Lubrizol under the designation AMPS.
The relative proportions of the water-soluble diacetone acrylamide monomer and the water-soluble comonomers that can be used depend upon the reactivity of these monomers as well as the desired properties of the resulting water-insoluble polymers. It has been found, however, that the amount of diacetone acrylamide present in the copolymers ranges from about 40 to about 95 weight percent of the polymer composition. Thus, broadly, the water-insoluble polymers of the invention comprise a major amount of at least one N-3-oxohydrocarbon-substituted acrylamide and preferably from about 60 to 100 weight percent diacetone acrylamide (DAAm) with the balance in copolymers being formed from at least one other water-soluble monomer.
The polymers of this invention can be formd in situ by injecting monomer solutions containing polymerization initiators into subterranean formations. The feasibility of polymerizing the monomers in situ, e.g., in saline connate waters is supported by the success of laboratory runs in Berea sandstone cores wherein the cores were plugged by injecting solutions of monomers and initiators. The cores were saturated with brine containing appropriate dissolved salts, such as found in sea water, to provide a simulated or synthetic sea water (SSW). Natural sea water and formation brines can also be used as the polymerization media in the core runs. Various field brines containing a high percentage of dissolved solids can be diluted with fresh water to provide an appropriate concentration of dissolved solids for lab core tests. Alternatively, salts can be added to various field brines, if deemed necessary, to obtain the desired salt level.
The following summary indicates representative monomer charges and initiators which are useful over a range of temperatures for permeability contrast correction as described in the instant invention.
______________________________________ Monomer Reservoir Charge Temp. °F. Initiator ______________________________________ 60-80 pts by wt DAAm 75-125 Amidino-type such 40-20 pts by wt Am as Wako-VA-044 and Wako V-50 and persulfates with or without added activators 60-80 pts by wt DAAm 125-175 Wako V-50, AIBN 40-20 pts by wt Am and azocyano- valeric acids 79-90 pts by wt DAAm 175-200 Wako V-50, AIBN 30-10 pts by wt Am and azocyano- valeric acids 80-95 pts by wt DAAm 175-200 Wako V-50, AIBN 20-5 pts by wt NaAMPS and azocyano- valeric acids 80-95 pts by wt DAAm >200 azocyanovaleric 20-5 pts by wt NaAMPS acids 40-80 pts by wt DAAm >200 azocyanovaleric 60-20 pts by wt VP acids ______________________________________
Oil field brines can be used as polymerization media in lab core runs. Such brines can be filtered or otherwise purified to remove undesirable solid matter before use in lab runs. Oil field brines can contain up to about 25 percent by weight of dissolved inorganic salts. In addition to NaCl, brines usually contain up to about 10 percent by weight of Ca++ and Mg++ based on the total amount of salts present. Small amounts of other soluble salts are also frequently present, e.g., NaHCO3, BaCl2, and the like. Typical brines contain from about 1 to about 14 weight percent dissolved salts based on water.
If the in situ polymerization is to be carried out at an offshore oil recovery site, natural sea water would be the preferred polymerization medium to use in simulated lab core runs. Sea water may require a preliminary treatment such as simple filtration to render it suitable for use as a polymerization medium in a laboratory core test.
The polymers of this invention can be prepared by processes using various free radical polymerization initiators known to those skilled in the art. Preferred initiators for the instant invention include chemical polymerization initiators.
Chemical polymerization initiators suitable for the inventive in situ polymerization process include azo compounds and organic peroxides such as 2,2'-azobis(isobutyronitrile) (commercially available as Vazo-64® from E. I. DuPont); 2-t-butylazo-2-cyanopropane, 2,2'-azobis(2,4-dimethylvaleronitrile) (Vazo-52® from E. I. DuPont), 2,2'azobis(2-amidinopropane)dihydrochloride (V-50 from Wako); 2-t-butylazo-2-cyanobutane; 2-t-butylazo-1-cyanocyclohexane; benzoyl peroxide; di-t-butyl peroxide; 2,2'-azobis(N,N-dimethyleneisobutyramidine)dihydrochloride(VA-044 from Wako); t-butylperoxy-acetate, t-butyl peroxypivalate, 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane (commercially available as Luazo®55 from Lucidol Div., Pennwalt Corp.); and hyponitrites such as t-butyl hyponitrite and t-amyl hyponitrite; 2-t-butylazo-2-cyano-4-methylpentane (Luazo®70); 4,4'-azobis(4-cyanovaleric acid); 4-t-butylazo-4-cyanovaleric acid and the like. The azo compounds are presently preferred for most applications, as some peroxides appear to have a tendency to adversely affect the polymer; however, some peroxides are effective at lower temperatures than those at which most azo compounds are useful.
A particularly suitable lower temperature initiator is 2,2'-azobis(2,4-dimethyl-4-methoxy-valeronitrile) commercially available as Vazo 33 from E. I. DuPont. Presently preferred initiators include t-butyl peroxypivalate (t-BPP), Luazo 55, Luazo 70, p-menthane hydroperoxide activated by FeSO4.7H2 O and especially 2,2'-azobis(isobutyronitrile) (AIBN). The use of these initiators usually results in the production of higher molecular weight polymers, Luazo 70 has been found to give excellent results because, as a liquid, it is more uniformly dispersible in water than are solid initiators such as AIBN. Luazo 55 is also a liquid and possesses the same advantage. The amidine type initiators and the 4-cyanovaleric acid initiators are preferred because they are water soluble. An inert atmosphere substantially free of oxygen or other known inhibiting materials should be provided when chemical polymerization initiators are used.
Chemical polymerization initiators which are substantially soluble in the polymerization media of this invention are advantageously used because they can be dissolved in the monomer solution or dispersed in a small amount of solvent which is miscible or soluble in the monomer solution therein before the monomer solution is injected into the subterranean formation.
Chemical polymerization initiators which are insufficiently soluble in the monomer solution of this invention in the concentration required for initiation can be added in the commercially available state or dispersed as a fine powder but are generally more effectively employed if first dissolved in a liquid which is soluble in or miscible with the monomer mixture. For example, a water-miscible solvent such as acetone or an alcohol can be used to solubilize 2,2'-azobis(isobutyronitrile), the preferred chemical initiator, and to disperse it in the aqueous monomer mixture.
Normally, about 0.05 to about 2 weight percent of chemical initiator based on total monomer weight is used for chemical initiation. The appropriate initiator is selected based on the temperature of the subterranean formation to be treated. For example, at a formation temperature of about 170 F., the initiator should have a half-life of at least several hours at 120 F.
The in situ polymerization of this invention is applicable to any situation where it is desired to selectively plug more permeable zones in subterranean formations by in situ polymerization of water-soluble monomers to form water-insoluble polymers. The invention is primarily directed to the selective plugging of the more permeable zones known as "thief" zones to improve the sweep efficiency of post-primary oil recovery processes. In accordance with the invention, one or more water-soluble monomers are injected as an aqueous slug into a subterranean formation passing predominantly into the more permeable zones of the formation wherein the monomers polymerize in situ and form water-insoluble polymers. Polymerization initiators can be injected preferably along with monomer(s). Alternatively, the initiators can be injected subsequently or prior to monomer injection.
Following injection of monomer or monomers and whatever induction time is required for in situ polymerization and plugging to occur, normal post-primary or enhanced oil recovery operations are then employed. For instance, conventional waterflooding can be commenced after a selective plugging operation is complete. With the more permeable zones selectively plugged, the subsequently injected drive fluids are diverted into the previously less permeable but relatively oil rich zones resulting in improved sweep efficiency and a lower water to oil ratio at the producing wells.
This example describes the experimental procedure which was used to substantiate operability in the present invention.
Epoxy wrapped Berea sandstone cores (1" diameter×3 inches long) which were equipped with pressure taps 1 centimeter from the face were evacuated, saturated and then pressure saturated with synthetic North Sea water (SNSW). The Berea cores were waterflooded at 150 F., with SNSW until a constant permeability was obtained. In one run (run 3, Table I), the core was oilflooded with crude NBU oil before waterflooding to residual oil saturation. The cores were generally conditioned in this manner before the injection of the monomer slugs containing polymerization initiators.
Two pore volume slugs of monomer/initiator were prepared for each core run. These solutions were purged with N2 for 20-30 minutes before being injected into the cores. After injection of the monomer slugs, the cores were allowed to stand without flow overnight (ca. 18 hours) at 150 F. during which time the in-situ polymerization occurred.
After checking the entrance and exit tubing of the cores to verify that they were not blocked, the pumping of SNSW was resumed at the same rate as had been used before the in-situ polymerization. A rapid rise in injection pressure and an increase in resistance factor signaled the success of the in-situ polymerization. In order to demonstrate the permanence or lack thereof concerning the effectiveness of the instant process, the passage of SNSW into the cores was continued and resistance factors and permeabilities were monitored.
In general, the effectiveness of the instant process can be expected to be greater for water soluble monomer(s) systems resulting in the production of insoluble polymers.
This example describes the results of selected Berea sandstone core runs in which in-situ polymerizations were carried out with selected monomers. The results are summarized in Table I.
TABLE I __________________________________________________________________________ Permeability Contrast Corrections in Berea Sandstone Cores by In-Situ Polymerizations Monomer Run Run Mix % By Wt. PV of Resistance Permeability Reference No. Type DAAm.sup.d VP.sup.e Am.sup.f Initiator SNSW.sup.i Factor (md) __________________________________________________________________________ 30655-7 1.sup.a Inv. 100 0 0 AIBN.sup.g 23.5 1.0 573# ACVA.sup.h 0.3 507 1 1.1 560.sup.j .sup. 1.sup.k 30655-22,23 2.sup.b Control 0 50 50 AIBN 11.3 1.0 538# ACVA <0.4 230 2 1.4 27 20 8.7 5.0 108 30 3.4 157 30655-25 3.sup.c Control 0 50 50 AIBN 3.6 1.0 134# ACVA <0.4 25 5 0.4 9 15 0.9 4.4 30 6.7 2.7 49 __________________________________________________________________________ #These numbers represent core permeabilities before the insitu polymerization treatment. .sup.a A 10 weight percent solution of diacetone acrylamide (DAAm), 0.5 phm AIBN (2,2azobisisobutyronitrile) and 2.4 phm ACVA [4,4azobis(4-cyanovaleric acid)] in SNSW was injected into a Berea sandstone core. .sup.b A solution containing 2.5 weight percent acrylamide (Am), 2.5 weight percent N--vinyl2-pyrrolidone (VP), 0.5 phm AIBN and 1.2 phm ACVA in SNSW was injected into a Berea sandstone core. .sup.c A solution containing 2.5 weight percent Am, 2.5 weight percent VP 0.5 phm AIBN and 1.2 phm ACVA in SNSW was injected into a Berea sandstone core. This core contained waterflood residual oil. .sup.d DAAm represents diacetone acrylamide. .sup.e VP represents N--vinyl2-pyrrolidone. .sup.f Am represents acrylamide. .sup.g AIBN represents 2,2azobis(isobutyronitrile). .sup.h ACVA represents 4,4azobis(4-cyanovaleric acid). .sup.i "PV of SNSW" represents "pore volumes of synthetic North Sea water". .sup.j Resistance Factor reflects the ratio of mobilities of the injected SNSW before and after the insitu polymerization, i.e., the "resistance" t fluid flow after insitu polymerization was about 560 times as great as th resistance to fluid flow before the insitu polymerization. .sup.k The permeability of the core before the insitu polymerization was 573 millidarcies and was decreased to one millidarcy after the treatment.
Referring to runs 1, 2 and 3, it is evident that the immediate effect of the monomer slug injection was to decrease the core permeability resulting in the genesis of significant resistance factors. It is noteworthy that this initial effect was greater in inventive run 1 because the homopolymer of diacetone acrylamide is water in-soluble compared to the 50/50 wt/wt VP/Am copolymer of control runs 2 and 3.
The continued passage of SNSW through the cores after the in-situ polymerization further demonstrates the persistent effect of the insoluble polymer generated in run 1. After the passage of 1.1 pore volumes of SNSW following the in-situ polymerization treatment of run 1, the resistance factor was 560 and the permeability was 1. At comparable stages in runs 2 and 3, respectively, 1.4 pore volumes and 0.9 pore volumes of SNSW following the in-situ polymerization treatment, the resistance factors were 27 and 9 whereas the permeabilities were 20 and 30. These data indicate that the longer lasting effect noted in run 1 can be attributed to the genesis of an in-soluble polymer in the Berea sandstone core. Continued passage of SNSW in control runs 2 and 3 resulted in lower resistance factors and higher permeabilities as expected with the water soluble VP/Am copolymer.
Since copolymers of diacetone acrylamide (DAAm) with VP or Am containing in the range of 40 to 95 weight percent DAAm are water insoluble, it is contemplated that copolymers of DAAm/VP and DAAm/Am can be advantageously used in the instant process. Representative copolymers of DAAm and Am exhibit a tendency to swell and therefore are presently preferred in the instant permeability contrast correction process. Suitable water-soluble comonomers to be used in conjunction with DAAm include VP, Am, sodium 2-acrylamido-2-methylpropanesulfonate (NaAMPS) and acrylonitrile (An) wherein the designation water soluble comonomer indicates that said comonomers exhibit solubilities of 5 or more grams of comonomer per 100 mL of water at 20° C.
Claims (18)
1. A method for permeability contrast correction operations involving in-situ polymerizaion to form water-insoluble polymers in remote subterranean areas which comprises
(1) injecting into high permeability subterranean strata an aqueous solution containing water-soluble monomers comprising a major amount up to 100 weight percent of at least one N-3-oxohydrocarbon-substituted acrylamide and the balance being at least one other monomer selected from alpha,beta-unsaturated amides, alpha,beta-unsaturated nitriles, vinyl-containing sulfonates and N-vinyl amides, and
(2) polymerizing said monomer(s) in the presence of a free radical polymerization initiator to form water-insoluble polymers in-situ.
2. A process according to claim 1 wherein the initiator is introduced into the formation subsequent to the injection of water soluble monomers.
3. A process according to claim 1 wherein the polymerization initiator is introduced into the formation along with the monomers in an aqueous solution.
4. A process according to claim 1 wherein the aqueous solution is a brine.
5. A process according to claim 1 wherein the N-3-oxohydrocarbon-substituted acrylamide is diacetone acrylamide which is polymerized to form a water insoluble homopolymer.
6. A processs according to claim 1 wherein a water insoluble copolymer is formed from diacetone acrylamide and at least one of acrylamide and N-vinyl-2-pyrrolidone.
7. A process according to claim 1 wherein said N-3-oxohydrosubstituted acrylamides have the structural formula ##STR12## wherein R and R2 are each selected from the class consisting of hydrogen and lower alkyl radicals containing 1 to 6 carbon atoms and R1 is selected from the class consisting of ethylene and lower alkyl-substituted ethylene radicals with the proviso that said N-3-oxohydrocarbon-substituted acrylamides contain 6 to 14 carbon atoms.
8. A process according to claim 7 wherein said N-3-oxohydrocarbon-substituted acrylamide is polymerized with a comonomer selected from at least one N-vinyl amide having the formula ##STR13## wherein R'2, R3 and R4 are selected independently from the group consisting of hydrogen and methyl and R'1 is selected from C1 to C3 alkyl groups and the groups R'2 and R'1 can collectively represent linear or branched divalent alkylene groups containing 2 to 4 carbon atoms.
9. A process according to claim 7 wherein said substituted acrylamide is copolymerized with alpha,beta-unsaturated amides having the formula ##STR14## wherein R5 is a 1-alkenyl radical selected from the group ethenyl(vinyl), propenyl, isopropenyl, 1-butenyl, 2-methyl-1-propenyl, 1-pentyl, 3-methyl-1-butenyl and 1-methyl-1-butenyl.
10. A process according to claim 1 wherein the polymerization initiator is a chemical free radical initiator.
11. A process according to claim 10 wherein the chemical initiator is selected from organic azo compounds, organic peroxides or redox systems.
12. A process according to claim 11 wherein the initiator is one of 2,2'-azobis(isobutyronitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-amidinopropane)dihydrochloride, and 2,2'-azobis(N,N'-dimethyleneisobutyramidine)dihydrochloride.
13. A process according to claim 1 for the production of a homopolymer of said N-3-oxohydrocarbon-substituted acrylamide by polymerizing same in the presence of one of organic azo compounds, organic peroxides or redox systems in an aqueous saline solution.
14. A process according to claim 1 wherein the polymerizing medium comprises at least one alkali metal salt electrolyte and at least one alkaline earth metal electrolyte.
15. A method of decreasing the permeability of a permeable zone in a subterranean formation which comprises introducing into said permeable zone:
(a) an aqueous solution containing water-soluble monomers selected from
(1) diacetone acrylamide, and
(2) about 40 to about 95 weight percent diacetone acrylamide, and the remainder one other water-soluble monomer selected from alpha,beta-unsaturated amides, alpha,beta-unsaturated nitriles, vinyl-containing sulfonates and N-vinyl-amides, and
(b) an effective amount of a free radical initiator to polymerize and solidify the aqueous mixture therein and decrease the permeability of the formation.
16. A process according to claim 15 wherein a homopolymer of diacetone acrylamide is formed in said permeable area.
17. A process according to claim 15 wherein a copolymer of diacetone acrylamide and at least one of acrylamide and N-vinyl-2-pyrrolidone is formed in said permeable area.
18. A process according to claim 15 wherein said aqueous solution is a brine.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/755,750 US4637467A (en) | 1985-07-17 | 1985-07-17 | Permeability contrast correction |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/755,750 US4637467A (en) | 1985-07-17 | 1985-07-17 | Permeability contrast correction |
Publications (1)
Publication Number | Publication Date |
---|---|
US4637467A true US4637467A (en) | 1987-01-20 |
Family
ID=25040494
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/755,750 Expired - Fee Related US4637467A (en) | 1985-07-17 | 1985-07-17 | Permeability contrast correction |
Country Status (1)
Country | Link |
---|---|
US (1) | US4637467A (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4947933A (en) * | 1989-01-03 | 1990-08-14 | Mobil Oil Corporation | Temperature activated polymer for profile control |
EP0592252A1 (en) * | 1992-10-09 | 1994-04-13 | Halliburton Company | Reducing gas coning and fingering in a hydrocarbon-bearing formation |
US5335726A (en) * | 1993-10-22 | 1994-08-09 | Halliburton Company | Water control |
US5358051A (en) * | 1993-10-22 | 1994-10-25 | Halliburton Company | Method of water control with hydroxy unsaturated carbonyls |
WO1995026455A1 (en) * | 1994-03-28 | 1995-10-05 | Allied Colloids Limited | Downhole fluid control processes |
EP0877147A1 (en) * | 1997-05-07 | 1998-11-11 | Halliburton Energy Services, Inc. | Method of plugging low temperature subterranean formation |
EP0879933A2 (en) * | 1997-05-12 | 1998-11-25 | Halliburton Energy Services, Inc. | Polymeric well completion and remedial compositions |
US5945387A (en) * | 1997-05-12 | 1999-08-31 | Halliburton Energy Services, Inc. | Polymeric well completion and remedial compositions and methods |
US20080115692A1 (en) * | 2006-11-17 | 2008-05-22 | Halliburton Energy Services, Inc. | Foamed resin compositions and methods of using foamed resin compositions in subterranean applications |
US20110079389A1 (en) * | 2009-10-06 | 2011-04-07 | Mackay Bruce A | Method for treating well bore within a subterranean formation |
US20110130505A1 (en) * | 1999-01-26 | 2011-06-02 | Ira John Westerman | Gypsum wallboard |
US8657005B2 (en) | 2010-04-30 | 2014-02-25 | Exxonmobil Upstream Research Company | Systems and methods for hydraulic barrier formation to improve sweep efficiency in subterranean oil reservoirs |
CN106401480A (en) * | 2016-11-29 | 2017-02-15 | 中国石油天然气股份有限公司 | Technology combining horizontal drilling and profile control blocking |
WO2019130253A1 (en) * | 2017-12-29 | 2019-07-04 | Eni S.P.A. | Method for controlling the permeability of a petroleum well |
CN110922952A (en) * | 2019-12-18 | 2020-03-27 | 成都新驱势石油技术开发有限公司 | High-temperature high-salinity reservoir polymer microsphere profile control and flooding agent and preparation method and application thereof |
Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3115930A (en) * | 1959-10-05 | 1963-12-31 | Pure Oil Co | Process for selectively treating subterranean formations |
US3152641A (en) * | 1960-01-11 | 1964-10-13 | Sinclair Research Inc | Method for polymerizing resin-forming materials in subterranean areas |
US3199588A (en) * | 1961-10-31 | 1965-08-10 | Sinclair Research Inc | Formation plugging method |
US3199589A (en) * | 1962-02-06 | 1965-08-10 | Sinclair Research Inc | Method for polymerizing resin-forming materials and use in subterranean areas |
US3277056A (en) * | 1963-11-27 | 1966-10-04 | Lubrizol Corp | N-3-oxohydrocarbon-substituted acrylamides and polymers thereof |
US3451480A (en) * | 1967-04-19 | 1969-06-24 | Calgon Corp | Friction loss reducing |
US3476186A (en) * | 1967-12-21 | 1969-11-04 | Union Oil Co | Recovery of petroleum by flooding with viscous aqueous solutions of acrylic acid-acrylamide-diacetone acrylamide copolymer |
US3542867A (en) * | 1967-09-27 | 1970-11-24 | Lubrizol Corp | Production of n-3-oxohydrocarbon-substituted acrylamides |
US3542875A (en) * | 1967-10-17 | 1970-11-24 | Lubrizol Corp | Purification and recovery of n-3-oxohydrocarbon-substituted acrylamides |
US3551384A (en) * | 1968-06-19 | 1970-12-29 | Calgon C0Rp | Water soluble polymers of diacetone acrylamide |
US3900069A (en) * | 1974-07-11 | 1975-08-19 | Union Oil Co | Recovery of petroleum by flooding with viscous aqueous solutions of acrylamide-diacetone acrylamide copolymers |
US3948783A (en) * | 1974-04-30 | 1976-04-06 | Calgon Corporation | Process for the secondary and tertiary recovery of petroleum |
US4031958A (en) * | 1975-06-13 | 1977-06-28 | Union Oil Company Of California | Plugging of water-producing zones in a subterranean formation |
US4070865A (en) * | 1976-03-10 | 1978-01-31 | Halliburton Company | Method of consolidating porous formations using vinyl polymer sealer with divinylbenzene crosslinker |
US4141416A (en) * | 1976-05-24 | 1979-02-27 | Union Oil Company Of California | Enhanced oil recovery using alkaline sodium silicate solutions |
US4190109A (en) * | 1978-10-11 | 1980-02-26 | Phillips Petroleum Company | Introduction and selective removal of debilitating agent for permeability correction |
US4359093A (en) * | 1980-11-21 | 1982-11-16 | Union Oil Co. Of California | Method for enhanced oil recovery in reservoirs containing dissolved divalent metal cations |
-
1985
- 1985-07-17 US US06/755,750 patent/US4637467A/en not_active Expired - Fee Related
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3115930A (en) * | 1959-10-05 | 1963-12-31 | Pure Oil Co | Process for selectively treating subterranean formations |
US3152641A (en) * | 1960-01-11 | 1964-10-13 | Sinclair Research Inc | Method for polymerizing resin-forming materials in subterranean areas |
US3199588A (en) * | 1961-10-31 | 1965-08-10 | Sinclair Research Inc | Formation plugging method |
US3199589A (en) * | 1962-02-06 | 1965-08-10 | Sinclair Research Inc | Method for polymerizing resin-forming materials and use in subterranean areas |
US3277056A (en) * | 1963-11-27 | 1966-10-04 | Lubrizol Corp | N-3-oxohydrocarbon-substituted acrylamides and polymers thereof |
US3451480A (en) * | 1967-04-19 | 1969-06-24 | Calgon Corp | Friction loss reducing |
US3542867A (en) * | 1967-09-27 | 1970-11-24 | Lubrizol Corp | Production of n-3-oxohydrocarbon-substituted acrylamides |
US3542875A (en) * | 1967-10-17 | 1970-11-24 | Lubrizol Corp | Purification and recovery of n-3-oxohydrocarbon-substituted acrylamides |
US3476186A (en) * | 1967-12-21 | 1969-11-04 | Union Oil Co | Recovery of petroleum by flooding with viscous aqueous solutions of acrylic acid-acrylamide-diacetone acrylamide copolymer |
US3551384A (en) * | 1968-06-19 | 1970-12-29 | Calgon C0Rp | Water soluble polymers of diacetone acrylamide |
US3948783A (en) * | 1974-04-30 | 1976-04-06 | Calgon Corporation | Process for the secondary and tertiary recovery of petroleum |
US3900069A (en) * | 1974-07-11 | 1975-08-19 | Union Oil Co | Recovery of petroleum by flooding with viscous aqueous solutions of acrylamide-diacetone acrylamide copolymers |
US4031958A (en) * | 1975-06-13 | 1977-06-28 | Union Oil Company Of California | Plugging of water-producing zones in a subterranean formation |
US4070865A (en) * | 1976-03-10 | 1978-01-31 | Halliburton Company | Method of consolidating porous formations using vinyl polymer sealer with divinylbenzene crosslinker |
US4141416A (en) * | 1976-05-24 | 1979-02-27 | Union Oil Company Of California | Enhanced oil recovery using alkaline sodium silicate solutions |
US4190109A (en) * | 1978-10-11 | 1980-02-26 | Phillips Petroleum Company | Introduction and selective removal of debilitating agent for permeability correction |
US4359093A (en) * | 1980-11-21 | 1982-11-16 | Union Oil Co. Of California | Method for enhanced oil recovery in reservoirs containing dissolved divalent metal cations |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4947933A (en) * | 1989-01-03 | 1990-08-14 | Mobil Oil Corporation | Temperature activated polymer for profile control |
EP0592252A1 (en) * | 1992-10-09 | 1994-04-13 | Halliburton Company | Reducing gas coning and fingering in a hydrocarbon-bearing formation |
US5335726A (en) * | 1993-10-22 | 1994-08-09 | Halliburton Company | Water control |
US5358051A (en) * | 1993-10-22 | 1994-10-25 | Halliburton Company | Method of water control with hydroxy unsaturated carbonyls |
WO1995026455A1 (en) * | 1994-03-28 | 1995-10-05 | Allied Colloids Limited | Downhole fluid control processes |
EP0877147A1 (en) * | 1997-05-07 | 1998-11-11 | Halliburton Energy Services, Inc. | Method of plugging low temperature subterranean formation |
EP0879933A2 (en) * | 1997-05-12 | 1998-11-25 | Halliburton Energy Services, Inc. | Polymeric well completion and remedial compositions |
EP0879933A3 (en) * | 1997-05-12 | 1999-01-20 | Halliburton Energy Services, Inc. | Polymeric well completion and remedial compositions |
US5945387A (en) * | 1997-05-12 | 1999-08-31 | Halliburton Energy Services, Inc. | Polymeric well completion and remedial compositions and methods |
US5968879A (en) * | 1997-05-12 | 1999-10-19 | Halliburton Energy Services, Inc. | Polymeric well completion and remedial compositions and methods |
US8592541B2 (en) | 1999-01-26 | 2013-11-26 | Omnova Solutions Inc. | Gypsum wallboard |
US20110130505A1 (en) * | 1999-01-26 | 2011-06-02 | Ira John Westerman | Gypsum wallboard |
USRE43168E1 (en) | 1999-01-26 | 2012-02-07 | Omnova Solutions Inc. | Polymeric latexes prepared in the presence of 2-acrylamido-2-methylpropanesulfonate |
US20080115692A1 (en) * | 2006-11-17 | 2008-05-22 | Halliburton Energy Services, Inc. | Foamed resin compositions and methods of using foamed resin compositions in subterranean applications |
US20110079389A1 (en) * | 2009-10-06 | 2011-04-07 | Mackay Bruce A | Method for treating well bore within a subterranean formation |
US8215393B2 (en) * | 2009-10-06 | 2012-07-10 | Schlumberger Technology Corporation | Method for treating well bore within a subterranean formation |
US8657005B2 (en) | 2010-04-30 | 2014-02-25 | Exxonmobil Upstream Research Company | Systems and methods for hydraulic barrier formation to improve sweep efficiency in subterranean oil reservoirs |
CN106401480A (en) * | 2016-11-29 | 2017-02-15 | 中国石油天然气股份有限公司 | Technology combining horizontal drilling and profile control blocking |
WO2019130253A1 (en) * | 2017-12-29 | 2019-07-04 | Eni S.P.A. | Method for controlling the permeability of a petroleum well |
US11624021B2 (en) | 2017-12-29 | 2023-04-11 | Eni S.P.A. | Method for controlling the permeability of a petroleum well |
CN110922952A (en) * | 2019-12-18 | 2020-03-27 | 成都新驱势石油技术开发有限公司 | High-temperature high-salinity reservoir polymer microsphere profile control and flooding agent and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0115836B1 (en) | Polymeres useful in the recovery and processing of natural resources | |
US4439334A (en) | Enhanced oil recovery methods and systems | |
US6030928A (en) | Polymers useful in the recovery and processing of natural resources | |
US5358051A (en) | Method of water control with hydroxy unsaturated carbonyls | |
US5382371A (en) | Polymers useful in the recovery and processing of natural resources | |
EP0651131B1 (en) | Control of water flow from subterranean formation | |
US4395340A (en) | Enhanced oil recovery methods and systems | |
US4637467A (en) | Permeability contrast correction | |
US4409110A (en) | Enhanced oil displacement processes and compositions | |
US4401789A (en) | Enhanced oil recovery methods and systems | |
AU718819B2 (en) | Blocking composition for use in subterranean formation | |
EP1193365B1 (en) | Reducing subterranean formation water permeability | |
US4439332A (en) | Stable emulsion copolymers of acrylamide and ammonium acrylate for use in enhanced oil recovery | |
WO2019079562A2 (en) | Performed particle gel for enhanced oil recovery | |
US3949811A (en) | Method for reducing the permeability of subterranean formations to brines | |
US4563290A (en) | Water-soluble copolymers useful for enhanced oil recovery | |
US5829527A (en) | Compositions and applications thereof of water-soluble copolymers comprising an ampholytic imidazolium inner salt | |
EP0399767A2 (en) | Interpolymers useful for treating subterranean formations | |
WO2019183390A1 (en) | Preformed particle gel for enhanced oil recovery | |
US4582137A (en) | Polymerizable surfactants for permeability control in waterflooding | |
US3400761A (en) | Use of fluid flow barriers in the secondary recovery of oil | |
US4163476A (en) | Secondary recovery process utilizing an acrylamido alkanesulfonic acid polymer | |
US4200151A (en) | Secondary recovery process | |
US6186231B1 (en) | Conformance improvement in hydrocarbon bearing underground strata using lignosulfonate-acrylic acid graft copolymer gels | |
WO1995026455A1 (en) | Downhole fluid control processes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: PHILLIPS PETROLEUM COMPANY, A CORP OF DE. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:WESTERMAN, I. JOHN;SHAW, JAMES E.;REEL/FRAME:004431/0991 Effective date: 19850712 |
|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
REMI | Maintenance fee reminder mailed | ||
LAPS | Lapse for failure to pay maintenance fees | ||
FP | Lapsed due to failure to pay maintenance fee |
Effective date: 19950125 |
|
STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |